Allyl esters of bicyclic carboxylic acids and polymers thereof



United States Patent 3,164,573 ALLYL ESTERS 0F BICYCLIC CARBOXYLIC ACIDS AND POLYMERS THEREOF George C. Schweiker, Mountainside, N.J., assignor to Velsieol Chemical Corporation, Chicago, 11]., a corporation of Illinois No Drawing. Filed Feb. 16, 1961, Set. No. 89,653

15 Claims. (Cl; 260-785) This invention relates to new chemical compounds and polymers thereof. More particularly, this invention relates to new allyl esters of bicyclic carboxylic acids and the polymeric compositions derived therefrom.

The new chemical compounds of the present invention have the following formula:

H H R f AA (CHr)n-COCH CH=CH; I h .A- AR 11 R wherein R isselected from the group consisting of hydrov The homopolymers of the present invention are unlike homopolymers of the vinyl esters of the bicyclicheptene acids. The vinyl esters of the class described cross-link upon polymerization to form hard, nonmoldable, solventinsoluble polymers. The homopolymers of the present invention, on the other hand, have low molecular weight, are readily moldable, and are soluble in the common aromatic hydrocarbon solvents. These differences between the homopolymers of the present invention and the homopolymers of the vinyl esters, also serve to point out the valuable advantages possessed by the homopolymers of this invention.

The compounds of the present invention wherein the As are an olefinic bond can be readily polymerized under polymerization conditions to produce valuable homopolymers soluble in the aromatic hydrocarbons, having low molecular weight, and the capability of being thermally treated to give hard insoluble products. These homopolymers have the desirable characteristics of being easily molded while in the soluble state and of being: permanently set at elevated temperatures, for example, between about ZOO-500 C. for several minutes, by being substantially crosslinked at the olefinic bonds. solution of these soluble homopolymers in aromatic solvent forms excellent coating which can be thermally set bybaking at elevated temperatures. 1

These cyclic unsaturated compounds can also be copolyinerized with similar polymerizable compounds, such as the vinyl aromatic compounds and the maleic acid or maleic anhydride type compounds, to yield copolymers having a wide and diverse range of properties.

The compounds of the present inventionwherein the Asare hydrogen, also form homopolymers which are soluble in the aromatic hydrocarbons. However, as these homopolymers lack sites for. crosslinking, they remain easily moldable and do not set at elevated temperatures. These compounds also can be copolymerized as described previously, yielding copolymers oftentimes having properties distinct from the properties of the cyclic unsaturated copolymers.

Thus, it is one object of the present invention to provide polymeric material, which can be easily molded and subsequently permanently set by thermal treatment.

gen and an alkyl group containing from 1 m4 carbon atoms, the As are selected from the group consisting of hydrogen and an olefinic bond, and n is an integer from 0 to 10.

The number ofreoccurring structural units (m) is directly related to the molecular weight of the'particular homopolymer; The number of reoccurring structuralunits in the individual molecules of the homopolymers of the present invention may vary from 2 to about 50.

Homopolymers of the present invention wherein (m) is ing the experimentallydetermined molecular weight of thegpolymer by the molecular weight of the monomeric compound. Thus it can readily be'seen thatffm. calculated in the above manner represents the averageinumber of units in the homopolymer molecule. i t.

It is another object of the present invention to provide polymeric material which is soluble in aromatic hydrocarbons before setting, and insoluble after setting. Another object of the present invention-is'toprovide monomeric compounds, which upon homopolymerization from homopolymers useful as angingredient in the manufracture of films and coatings. p

Still another object of the-present invention is to provide copolymeric material useful in the production of a variety of films, coatings, and molded products.

These and other objects of the present invent-ion will be apparent from the ensuingdescription. v

The new ester compounds of; the. present invention can be readily prepared by esterification of the corresponding bicyclicacid. Bicyclic acids usable herein can be pre% pared by a Diels-Alder adduction of cyclopentadiene as the diene and as the dienophile, the proper monounsaturated aliphatic acid, such as acrylic acid, methacrylic acid, crontonic acid, ,8,,B-dimethylacrylic acid, vinylacetic acid,

'fl-n etliylvinylacetic acid," tiglic acid, -y,'.y-d irnethylvinyl 7 Furthermore, a

palladium or platinum on charcoal.

catalysts.

acetic acid, allylacetic acid, 'y-methylallylacetic acid, methylcrontonic acid, ethylcrotonic acid, S-hexenoic acid, 9- decenoic acid, 10-undecenoic acid, and the like. The'bicyclic-heptene acid thus formed, can be esterified directly with allyl alcohol, to form the compounds of this invention wherein the As are an olefinic bond, or can be estertfied by any other method known to the art.

The bicyclic-heptene acid can be readily hydrogenated to form the bicyclic-heptane acid, which in turn can be esterified with allyl alcohol to form the allylester compounds of the present invention, wherein the As are hydrogen.

Specifically, the Diels-Alder adduct of cyclopentadiene and the proper monounsaturated aliphatic acid can be prepared by any of the means common tothe art. For.-

7 example, bicyclo[2.2.l]hept-S-en-2-carboxylic acid can be prepared by contacting acrylic acid and cyclopentadiene at about 25 75 C. until the reaction ceases to be exothermic. Bicyclo[2.2.1]hept-5-en-2-acetic acid can be prepared by the method just described or by preparing the corresponding bicyclo[2.2.1]hept-S-en-Z-acetonitrile by reacting allyl cyanide with cyclopentadiene in a pressure bomb, treating the acetonitrile with an alkali metal hydroxide, such as sodium hydroxide, and acidifying with a mineral acid to yield the desired bicyclo[2.2.1]hept-S- en-Z-acetic acid.

To obtain the saturated cyclic acids, the unsaturated cyclic acid thus'produced is hydrogenated with hydrogen gas in the presence of a hydrogenation catalyst, such as The newestersiof the present invention can be readily produced by direct esterification of the proper acid with allyl alcohol injtheipresence of an acidic catalyst, such as paratoluenesulfonic acid. Alternatively, the new est'ers can be produced'by converting the proper bicyclic flC'idlOl its alkali metal salt by treatment with an alkali metal hydroxide, such as potassium hydroxide, and reacting the isolated acid salt with allyl chloride in a refluxing solvent, such as methanol. The ester of the present in-v vention is then recovered'by the commonly known processes of solvent stripping, extraction from water, and drying, or by any of the other'concentration processes common to the art.

The homopolymers of the present invention can'readily be prepared by many of the polymerization processes known to the art, such as by the'bulk, solution, or emulsion processes. The polymerization of "the esters of this inventionby the said processes requires apolyme'rization catalyst, such as the peroxide catalysts, or the redox" An 'example'o f a peroxide catalyst is benzoyl peroxide, while an example of a redox catalyst system is an aqueous solution of ferrous sulfate 'heptahydrate, p0

'tas'sium persulfate, and sodium' bisulfate. -A suitable The temperature of themixabout 30% by weight monomer in solvent has been found satisfactory. The solution is heated to reflux and refluxing is continued until the polymerization is complete. The homopolymeric product thus produced can be readily isolated from the solvent solution by mixing the solution with an excess of a solvent in which the product has decreased solvency, such as pentane, and separating the precipitated hompolymer therefrom. The homopolymer is next dried by vacuum, low heat, or a combination of the two, to yield the dry valuable product.

Emulsion polymerizations are readily performed by agitating an ester of the present invention with water, catalyst, and a small quantity of an emulsifier. Suitable portions of reactants are: allyl ester as described herein, 10-40 parts by weight; water, 10-40 parts by weight; catalyst, 0.1-l0 parts by weight; and emulsifier, 0.054 parts by weight. Suitable emulsifiers for this polymerization reaction are the anionic type emulsifiers such as sodium stearate, potassium laurate, morpholine laurate, sodium lauryl sulfate, sodium Z-ethylhexyl sulfate, sodium naphthalenesulfonate, sodium alkylnaphthalene sulfate, and the like. The emulsion is heated for several hours. The total reaction mixture is poured into an excess amount of a solvent in which the polymer has decreased solvency, such as pentane, to precipitate the homopolymer of the present invention. The dry polymer isisolated by filtering the precipitate and drying at atmospheric or subatmospheric pressure. v t

The polymerizations as described herein proceed readily at atmospheric pressure at temperatures from about 25 C. to about 200 C. A preferable reaction temperature is from about 75 C. to about 150 C. Super'atmospheric pressures can be used with'equal success. Increasing the temperature of the polymerization has the effect of decreasing the time required and increasing thermal crosslinking in polymers containing the cyclic olefin bond. Increases in the time ofpolymerization result in higher yields of polymer, within a maximum limit. Increasing the concentration of the catalyst increases the conversion ofmonomer up to a limiting concentration and decreases the time required for polymerization. The use of a solvent decreases thermal crosslinking, but also greatly decreases the yield of polymer and requires a longer time and larger amount ofcatalyst.

are the vinyl aromatic compounds of the formula maintained to control the course of the poiymerization.

The reaction is deemed complete when the reaction ceases and can no longer be sustatined at slightly increased ternpratures. ;The homopolymeric product can be recov-' 'ered by simply pouring the products out of the reaction vessel if the product is a liquid, or if solid, the solid can be dissolved in a suitable solvent, such as benzene, and precipitated from an excess of a solvent such as pentane, in which the 'homopolymeryhasdecreased solvency.

Solution polymcrizations'are readily 1 erformed by dis:

solving acompound of the present invention-and catalyst,

asf-heretofore described, in a solvent, such as benzene.

HCIl=CHz wherein Y is selected from the group consisting of chlorine, bromine, carbcxyl, methyl, ethyl, and rnixtures thereof, and x is an integer from .0, to 2; and the compounds of the formula wherein Risselected from the group'consisting of hydrogen and al-ltyl radicals containing 1 to 4 carbonatoms and their anhydrides.

- Examples offsuitable vinyl aromatic compounds are:

styrene, vinyltolue'he,vinylxyl'ene, vinylchlorobenzene, vinylchlorotoluene;vinylethylbenzene, vinylbenzoic acid,

and vinyldichloroberiz'ene. I Examples of the latter class of suitable compounds arez "'malei'c' acid, .maleic. anhydr de, .citraconic acid, citraeonic*a 75.

nhydride, cisraconitic acid, and cis-aconiticanhydride; 1

The followng examples are presented to illustrate the preparation of the allyl esters, the homopolymers, and the copolymers of the present invention.

EXAMPLE 1 Preparation of Bicycl[2.2.1]Hept-5-En-2-Carb0xylic Acid Into a 300 ml. three-necked, round-bottom flask equipped with a stirrer, thermometer, condenser, and addition funnel, was placed acrylic acid (158 gm.; 2.1 mols). Cyclopentadiene (165 gm.; 2.5 mols) was slowly added from the addition funnel over a period of one hour While the contents of the flask were vigorously stirred. The temperature Was maintained at 35-40 C. during the addition by use of a water bath. Stirring was continued until the exotherm ceased to be apparent. The solution was allowed to stand for three days, was then distilled under reduced pressure, and the fraction boiling at 126-128 C. at 12 mm. mercury collected and redistilled to obtain an 80% yield of bicyclo [2.2.1]hept--en- 2-carboxylic acid, boiling at 85 C. at 0.6 mm. mercury.

EXAMPLE 2 Preparation of Allyl Bicyclo [2.2.1]Hept-5-En-2-Carboxylate Into a 500 ml. three-necked, round-bottom flask equipped with a thermometer, a Dean-Stark trap, and a condenser, were placed bicyclo[2.2.1]hept-5-en-2-carboxylic acid (81 gm.; 0.59 mol), allyl alcohol (58 gm.; 1 mol), paratoluenesulfonic acid (2 gm.), and benzene (200 ml.). The solution Was heated at reflux with the water produced by the reaction being collected in the Dean-Stark trap. The reaction was allowed to continue for 22 hours. At the end of this period, the solution was cooled and the benzene solvent removed by distillation at atmospheric pressure under a blanket of nitrogen gas until a pot temperature of 135 C. was reached. The residue was then distilled in vacuo to obtain allyl hicyclo[2.2.1Jhept-S-en-Z-carboxylate, a colorless liquid boiling at 102-106 C. at 12 mm. mercury. V

The product had the following elemental analysis as calculated for C I-1 0 Theoretical, percent Found, percent EXAMPLE 3 Preparation of Bicyclo[2.2.1]Hept-5-En-2-Acetonitrile EXAMPLE 4 7 Preparation of Bicyclo[2.2.1]Hept-5-En-2-Acetic Acid Into a 500 m1. three-necked, round-bottom flask equipped With a reflux condenser were placed bicyclo[2.2.1]hept-S-en-Lacetonltrile (90 gm.; 0.67 mol; prepared in Example 3), sodium hydroxide (80 gm.; 2 mols), and water (250 ml.). The mixture was heated at reflux for 24 hours, at which time ammonia gas ceased "to exude therefrom. The solution was cooled and acidified by adding incremental quantities of hydrochloric acid. The

' product acid was extracted from the reaction solution with portions of diethyl ether (150 ml.). The ether extract 6 was Washed with water (50 m1.), dried over anhydrous magnesium sulfate, and filtered from the solid drying agent. Ether was removed from the extract on a steam bath and the residue distilled in vacuo to yield bicyclo[2.2.1]hept-5-en-2-acetic acid, boiling at 148-155 C. at 19 mm. mercury.

EXAMPLE 5 Preparation of Allyl Bicyclo[2.2.1]Hept-5-En-2-Acetate Into a 500 m1. three-necked, round-bottom flask equipped with a thermometer, a Dean-Stark trap, and a condenser, were placed bicyclo[2.2.1]hept-5-en-2-acetic acid (65 gm.; 0.43 mol; prepared in Example 4), allyl alcohol (30 gm.; 0.52 mol), paratoluenesulfonic acid (1 gm.), and benzene (250 ml.). The solution was heated at reflux for 22 hours with the water produced by the reaction being collected in the Dean-Stark trap. At the end of this period, the solution was cooled and the henzene solvent removed by distillation at atmospheric pres sure under a blanket of nitrogen gas until a pot temperature of 135 C. was reached. The residue was then distilled in vacuo to yield allyl bicyclo[2.2.l]hept-5-en-2 acetate, a colorless liquid boiling at 131-133 C. at 22 mm. mercury.

The product had the following elemental analysis as calculated for C H O Theoretical, percent Found, percent EXAMPLE 6 Preparation of 2-Melhyl-Bicycl0[2.2.1]Hept-5-En-2- CarbOxylic Acid Into a one-liter three-necked, round-bottom flask equipped with stirrer, condenser, thermometer, and addition funnel, were placed methacrylic acid (478 gm.; 5.6 mols) and hydroquinone (1 gm). Cyclopentadiene (366 gm.; 5.6 mols) was added to the flask through the addition funnel over a period of one hour, while the reaction solution was heated to a temperature of 37 C. by means of a heating mantle. Thereafter, the heat of the reaction maintained the reaction temperature at 3739 C. for 6 hours. The reaction solution was allowed to stand for 16 hours, after which it was distilled in vacuo to yield 2-methylbicyclo 2.2. l ]hept-5-en-2-carboxylic acid, which boiled at 128l34 C. at 12-14 mm. mercury.

EXAMPLE 7 Preparation of Allyl 2-Methyl-Bicyclo[2.2.1]Hept-5- En-Z-Carboxylate 2-methylbicyclo[2.2.1]hept-5-en-2-carboxylic acid (109 gm.; 0.71 mols) was dissolved in methanol (200 ml.) and a solution of potassium hydroxide (40 gm.; 0.71 mols) dissolved in methanol (150 ml.) was added to it. The methanol was removed under vacuum and the residue was air-dried to yield 135 gm. of the potassium salt of the acid, which was then dissolved in methanol (200 ml.) and poured into a 500 ml. three-necked, round-bottom flask equipped with a mechanical stirrer, reflux condenser, and internal thermometer. Allyl chloride (60 gm.; 0.78 mols) was added to the flask, and the contents heated at reflux for 17 hours by means of a heating mantle. The methanol was removed by distillation at atmospheric pressure under a blanket of nitrogen. The residue was mixed with Water ml.) and extracted with diethyl ether (200 ml.). The ether layer was then separated from the aqueous layer, dried over anhydrous magnesium sulfate, filtered, and distilled on a steam bath to remove the ether solvent. The residue therefrom was distilled in vacuo to yield allyl boiled at l07111 C. at 17 mm. mercury.

Theoretical, percent 74. 96 Found, percent 74. 54

EXAMPLE 8 Preparation of Bicyclo[2.2.1]Heptan-2-Carb0xylic Acid In to a 500 ml. glass pressure bottle Was placed bicyclo [2.2.1]hept--en-2-carboxylic acid (138 gm.; 1 mol), methanol (50 ml.) and palladium on carbon catalyst (2 gm.). The bottle was placed in a Parr hydrogenation apparatus, evacuated, and was pressured with hydrogen gas to 40 pounds per square inch 3 times, until hydrogen ceased to be taken into the reaction mixture. The bottle Was removed from the apparatus and the catalyst separated from the reaction solution by filtration through a bed of hydrated amorphous silica. The reaction solution'was poured into a 500 ml. distillation flask and the methanol solvent removed by atmospheric distillation and thenby an aspirator. The residue was distilled in vacuo to yield bicyclo[2.2.1]heptan-2-carboxylic acid, boiling at 9299 C. at 0.050.07 mm. mercury.

EXAMPLE 9 7 7 Preparation of Allyl Bicyclo[2.2.1]Heptan-2Carb0xylate Into a 500 m1. three-necked, round-bottom flask equipped with a thermometer, Dean-Stark trap and condenser, Were placed bicyclo[2.2.l]heptan-2-carboxylic acid (35 gm; 0.25 mol), allyl alcohol (17 gm.; 0.3 mol), paratoluenesulfonic acid (1 grim), and benzene (2250 ml.) The reaction mixture was heated at reflux for 12 hours, while the water produced by the reaction was collected in the Dean-Stark trap. The apparatus was-modified for distillation, and most of the benzene was removed by atmospheric distillation.v The residue was dissolved in diethyl ether (50 1111.), Washed several times with a 10% solution of sodium bicarbonate and Washed with water. The ether solvent was removed by atmospheric distillation, and the residue was distilled in vacuo to yield allyl bicyclo[2.2.1]- heptan-E -carboxylate, which boiled at 123-125 C. at 26 mm. mercury and solidified'upon cooling.

EXAMPLE 10 Preparation of Bicycle[2.2.1]Heptan-Z-Acetic Acid Into a 500 ml. glass pressure bottle was placed bicyclo [2.2.1]hept-5-en-2 acetic acid (153 gm; 1 mol), methanol (100 ml.), and 10% palladium on carbon catalyst (2 gm.). The bottle was placed into a Parr hydrogenation apparatus, evacuated, and pressured with hydrogen gas to 40.

\ {2.2.11heptan-2-aicetic acid, boiling at 153156 C. at 18 mercury. I

v 7 EXAMPLE 11 Preparation of Ailyl Bicyclo[2.2.1]Heplan-2-Acetatc Bicyclo[2.2.1]he tan-Z-acetic acid 485 .gm.', 0.25

mol), allyl alcohol (17 gm.; 0.3 mol), paratoluenesulfonic'acid (1 gin), and'benzcne (2501 11.) are charged into a 500 ml. three-necked, round-bottomfiask equipped with a j'thermometer, Dean-Stark trap and condenser. The reaction solution is'fheated" at reflux .for about 20 can be reacted'with the designated dienophile to form the corresponding bicyclic acid, which in turn is reacted with allyl alcohol (denoted by A) to form the desired ester of the present invention. Example 12 illustrates the preparation of several of the other esters of the present invention:

EXAMPLE 12 Dienophole Alcohol Ester +Orotouic Acid.

+Allylacetic Acid +Methylviny1acctic Acid.

+3-Pentenoic Acid +A...

+Senecioic Acid +Tiglic Acid +A +Allylpropi0nic Acid -Mcthy1 allylacetic Acid.

I +4-Hcxenoic Acid +A.

' pionato.

acetate. =Allyl Z-Ethylbicyclo [2.2.11-hcpt-5-cn-3- acetate.

=Allyl Bicyclo[2.2.l]hept- 5-eu-2-valerate.

= Allyl 2-M ethylbi cyclo [2. 2.1]hept-5-cn-2-butyrate. =Al1yl Z-Methylbicyclo [still-hept-5-en-3-hutyra =Allyl 2, 2-Dirncthy1bioyclo[2.2.1]hept5-cn-3- propionatc. =Al1yl Bicyclo[2.2.1]hcpt- 5-cn-2-caproate. =Allyl 2-Isopropylbicyclo [2.2.1]hept-5-en-3-propionate. =A1ly1 Bicycl0[2.2.l]hept- 5-en2-caprylate.

=Ally1 2-l'iiethylbicyclo [2.2.11-hcpt-5-en-3- oenanthylate. =A1lyl Bicycle [2.2.1]hcpt- 5-e1r2-pelargouate. =Allyl 2-Mcthy1bicyclo [2.2.11-hept-5-cn-3- caprylate.

+Pyroterebic Acid... +A.

+Hydr0sorbic Acid +A +4-Vinylvalcric Acid- +5-Methyl-5-hexcnoic Acid.

+4-Hcptenic Acid |A +3-Isoheptenic Acid. V-I-A.

+6Octenic Acid +s-Iso ecteiiidiicidnfl- +9-Deccnoic Acid +Isodccylenic Acid.

+9-Uudccylcnic Acid. Q

+8-Undecylenic Acid.

The method of Examples 1 and 5 can be utilized to prepare the bicycloheptane acids, which can then be esterified by the method of Example 2 to prepare the bicycloheptane allyl esters of the present invention. Thus, cyclopentadiene (denoted by fC) can be reacted with the designated dienophile to form the corresponding hicy-cloheptene acid. This unsaturated acid is hydrogenated with hydrogen gas (denoted by l-l to form the corresponding bicycloheptane acid, which is esterified with allyl alcohol (denoted by A) to produce the bicycloheptane allyl esters of the presentinvention. Example 13 illustrates the preparation 'of'several of thebicycloheptane allyl estersof-the present invention. 1

wherein in is aninteger from to V The above bullcpolymerization was repeated utilizing" 0.25 gm. ofbenzoyl peroxidel and aireaction time of 2 EXAMPLE 13 Diene Dienophile Hydrogen Alcohol Ester C +MethacrylicAcid +H +A =Al1y12-Methylbicyclo [2.2.1]-heptan-2-carboxylate O +Croton1cAc1d +H +A =Allyl 2-Methylbicyclo [2t.2.1]-heptan3-carboxy1- a e. C +Ally1aceticAc1d +H +A =Allyl Bicyclo[2.2.1]heptan- 2-propionate. G +Metl1ylvh1yl-acetic +H +A =Allyl 2-Methy1bicyclo Acld. [2.2.1]-heptan-2-acetate. C +3-Pentenoic Acid +H +A =Allyl Z-Methylbicyclo [2.2.1]heptan-3-acetate. G +Senecic Acid +H +A- =Ally12,2-Dimethylbicyclo [215.21]heptan-3-carboxyla e. C +TiglicAcid +H +A =Allyl 2,3-Dimethylbicyclo [2t.2.1]heptan-2-carboxylae. O +Ally1propionic Acid +H +A- =AllylBicyclo[2.2.1]heptan- 2-butyrate. C +-y-Methyl allyl-acetic +H +A y12-Methylbicyc1o[2.2.1]-

Acid. heptan-Z-propionate. O +4-HexoniocAcid +H +A =Allyl 2-Methylbicyclo [2.2.1]heptan-3-propionate G +PyroterebicAcid +H +A =Allyl 2,2-Dimethylbicyclo [2.2.1]heptan-3-acetate. C +Hydxos0rbicAcid +H +A =Allyl2-Ethylbicyclo[2.2.1]-

heptan-3-acetate. C +4-VinylvalericAcid +11 +A =A1ly1l Biyc1o[2.2.1.]heptan- -va era O +5-Methyl-5-hexenoic +H +A =Allyl 2-"vlethylbicyclo Acid. [2.2.1]heptan-2-butyrate. (J +4-Heptenic Acid +11 +A =Allyl Z-Methylbicyclo I [2.2.1]heptan-3-butyrate. C +3-Isoheptenic Acid +H +A =Al1yl 2,2-Dimethylbicyclo [2.2.1]heptan-3-propionate C +6-OctenicAcld +H +A =Allyl Bicyclo[2.2.l1heptan- Z-caproate. C +3-Isooctenic Acid +H +A =Allyl Z-Isopropylbicyclo [2.2.1]heptan-3-propionate C +9-Decenoic Acid +H +A- :Allyl Bicyc1o[2.2.11heptan- 2-capry1ate. C +IsodeeylenicAcid +H +A =Allyl 2-l\lethy1bicyelo[2.2.1]-

heptan-3-oenanthylate. G .t +9-Undecylenic Aeid +H +A. =Al1yl Bicyclo[2.2.1]heptan- 2-pelargonate. G +8-UndecylenicAcid +11 +A =Allyl 2-Metl1ylbicyclo [2.2.1]heptan-3-caprylate.

EXAMPLE 14 only /2 hour produced a homopolymer having a molec- Preparation of the Homopolymer of Allyl Bicycle Y [2.2.1]Hept-S-En-Z-Carboxylate Allyl bicyclo[2.2.1]hept-5-en-2carbbxylate -(5 gm.)

and benzoyl peroxide (0.05 gm.) were placed into an 18 x 150 mm. test tube. constant temperature bath at 99 C. for 6 hours. The polymer thereby produced has a softening point of C. and is free flowing at 100 C., as determined on a Fisher-Johns melting point apparatus; and is soluble in the aromatic solvents. Upon heating the polymer above 250 C., the polymer cured to a hard resin, which was insoluble in the aromatic solvents;

The homopolymer of allyl bicyclo[2.2.1]hept-5 en-2- carboxylate has reoccurring structural units of -the formula hours. Thefpolymer' 'tli'uis produced had amolecular weight of 920' as determined -cryoscopically,' .Tand an Ostwald viscosity (1% solution) at 25 C. K of; 0.04.

Uponinc-reasing the catalyst concentration to 0.5 gm the molecular weight of thelpolymer increased to 1625; This latter concentration of "catalyst and monomer, reacted for The test tube was placed in a bility.

ular weight of 1400, as determined cryoscopically. A fifth polymerization using 0.25 gm. of azo-bis (isobutyronitrile) was performed at 80 C. for 6 hours and produced a homopolymer having a molecular weight of 1240, as determined cryoscopically.

Films were prepared from the above homopolymers by dissolving the' homopolymer in xylene to form a 6% solution which wastcoated onto tin plate by a doctor blade set at 3 mils. The coated plate was placed under a. heat lamp for 5 minutes and then heated in an oven maintained at 400 F. for five minutes to thermally set the-coating. The filnrthereby produced has good adhesion and flexi- EXAMIPILE 1s; 4

Prepara'r i o'ri 5f the Homopolynier of Allyl Bicyclo [2.2.11H2pt-5-Ery2 Acetate .itAllyl bicycle[2.2.1]hept-5-en-2-acetate 1"(5 gin) and .benzoyl peroxide (0.25 gm.) were reacted for 2 hours as described in Example 14 to yield ahomopolymer having a softening point of 35 C. as determined on a Fisher- Johns melting point apparatus, and a molecular weight of 316 25 as determined' cryoscopically- T-he homopolymer also cured/to an insoluble,hardpolymer'uponheatingfto temperatures above 2 7 0. "C. A secondidentical polymerization produceda homopolymer having a molecular I weight of 2100. Upon reaction of 5 gms of the ester with 0.5 gm. benzoyl peroxide at 99 C. 'for only 1.5 hours; a homopolymer having a molecular weight of 1700 was produced. Thisjlatter homopplymer was dissolved in xylene to "form a' 20%. solution which was coated upon a tin plate as desc'rib'edi'n the previousjexample. The coating thus produced and cured hadex'cellent adhesion and flexibility,jeven after the coated tin platewas formed into a lid for a tincan.

-tions described herein.

' Preparation "invention;

, Preparation of a copolymer f l 1 The homopolymer of allyl 1bicyclo[2.2.1]hept-5-en-2- acetate has reoccurring structural units of the formula wherein m is :an integer from to 25.

'EXAMPLE 16 Preparation of a Homopolymer 0f Allyl Z-Methylbicyclo [2.2.] 1H apt-'5 -En-2-Carb0xylate Allyl Z-methylbicyclo [2.2. l hept-5-en-2-carboxylate (5 gm.) and ibenzoyl peroxide (0.25 gm.) were placed into an 18 x 150 mm. test tube. The test tube was placed in aconstant temperature bath at 99 C. for 1 hour. The

homopolymer thus produced had a softening point of 55 C. and a molecular Weight of 1700 as determined cryoscopically. The homopolymer flowed freely at 100 C.,

was soluble in the aromaticsolvents, and thermally cured to a hard insoluble polymer at temperatures above 235 C.

The homopolymer of allyl Z-methylbicyclo[2.2.1]hept- 5-en-2-carboxylate has reoccurring structural units'of the formula H H H H----H wherein m is an integer from 5 to 25.

, EXAMPLE -17 7 Preparation of a Momopolymer of Allyl Bicycl0-[2.2.Z]Heplun-2:/1cetate I Allyl bicyclo[2.2.l]heptan12 acetate (5 gm.) and benzoyl peroxide (0.25 gm.) are placed into an 18 x 150 mm. test tube. The" test tube is placed intoa constant temperature bath at 100 C. for 2 hours. The polymer thus produced is soluble, in the aromatic solvents and does not thermally set upon curingatincreased temperatures.

'IHomopolyniers of the other allyl esters of the present are placed into an 18 x 150 mm. test tube. The test tube is placed in a constant temperature bath at 100 C. for 8 hours to form the desired copolymer of the present invention.

Similarly, the other copolymers of the present invention can be prepared by reacting anally-l ester of the present invention with a polymeriz able compound as herein described.

"The homopolymers of the present invention possess valuable utility as ingredients in adhesivesand as films and surface coatings. This utility is enhanced by the solubility of the polymers in the aromatic solvents, their relatively low molecular Weight, their ability to be easily molded, and the ability of the polymers of the bicyc1oheptene-allyl esters to thermally cure into hard, insoluble, higher molecular Weight products. f

The copolymers of the present invention can have a Wide range of properties, and are thereby useful in various areas of application. Copolymers of the present invention, for example, are useful in the manufacture of pressure sensitive adhesives, wherein a solution of the I copolymer in aromatic solvent, such as xylene, is coated on a tile or other article andcovered with a vegetable parchment paper as a backing. The backing is then stripped off and the tile placed into position. Upon thermal treatment, the tile is permanently bonded to the base material. a

I claim:

1. A compound of the formula:

V H R H (H) H.- .(CH2) n-o-fo-orrroneom H R H formula invention can be readilyv prepared by the method described in Examples 14-117 orby the other polymerization reac- EXA PLE 18 I "S-enFZ-CarbOxyIate and Styrene of a cepol mgr f Allyl Bicycl0[2.2 .1]Hept-" 1 bicyclo[2.2.1]hept-5;en-2 carhoxylate (3.16 gm [styrene 1.84 gm.)',- ;and ben'zoyl peroxide" (O.275gm.)

are placed into an'IS'X 150 mm. test tube. The test tube is: placed in aconstant temperature bath" at 100 i for 6 hours to form the desired copolymer of the present Emir tei913 Li -Enp-Z-Aget'zzie and M q leicAc id wherein R selected the groupiconsisting of hydrogen andan alkyl 'groupcontai'ning fromjl to; '4 carbon atoms, mis'an integer from O'to 1, provided that when iz is 0a earbon-to-carbonfdouble bond is present between the .5 and -position rin'gcarbon-atoms, and- 1 is-aninteger from 0 to 10.

, 18,; newzcomposition' oi -matter comprisingf'a solid homopolymer of allyl bicyclo[2.2.1Jhept-S-en-Z-carboxylate having reoccurring structural units of the formula wherein m is an integer from 5 to 25.

10. A new composition of matter comprising a solid homopolymer of allyl bicyclo[2.2.1]hept-S-en-Z-carboxylate having reoccurring structural units of the formula wherein m is an integer from 5 to 25.

11. A solid, aromatic hydrocarbon insoluble polymer prepared by heating a homopolyer of claim 7, wherein m is 0 and a carbon-to-carbon double bond is present between the 5- and 6-position ring carbon atoms, at a temperature of between 200 C. and 500 C.

12. A solid copolymer formed by reacting under polymerization conditions in the presence of a free radical polymerization catalyst at a temperature of from about 25 C. to about 200 C., a compound of claim 1 with a compound of the formula wherein Y is selected from the group consisting of chlorine, bromine, carboxyl, methyl, ethyl, and mixtures thereof; and x is an integer from 0 to 2.

13. A new composition of matter comprising a solid copolymer formed by reacting a compound of claim 1 with styrene under polymerization conditions in the presence of a free radical polymerization catalyst at a temperature of from about 25 C. to about 200 C.

14. A new composition of matter comprising a solid copolymer formed by reacting under polymerization conditions in the presence of a free radical polymerization catalyst at a temperature of from about 25 C. to about 200 C., a compound of claim 1 with a compound having the formula wherein R is selected from the group consisting of hydrogen and an alkyl radical containing from 1 to 4 carbon atoms, and their anhydrides.

15. A new composition of matter comprising a solid copolymer formed by reacting a compound of claim 1 with maleic acid under polymerization conditions in the presence of a free radical polymerization catalyst at a temperature of from about 25 C. to about 200 C.

References Cited in the file of this patent UNITED STATES PATENTS 3,033,848 Caldwell .Q May 8, 1962 FOREIGN PATENTS 582,721 Great Britain Nov. 26, 1946 

1. A COMPOUND OF THE FORMULA:
 14. A NEW COMPOSITION OF MATTER COMPRISING A SOLID COPOLYMER FORMED BY REACTING UNDER POLYMERIZATION CONDITIONS IN THE PRESENCE OF A FREE RADICAL POLYMERIZATION CATALYST AT A TEMPERATURE OF FROM ABOUT 25*C. TO ABOUT 200*C., A COMPOUND OF CLAIM 1 WITH A COMPOUND HAVING THE FORMULA 